1. Field of the Invention
The present invention relates to a method of producing cyclododecanone and cyclododecanol. More particularly, the present invention relates to a method of producing cyclododecanone and cyclododecanol by a catalytic reaction of an epoxycyclododecane compound with hydrogen. Cyclododecanone and cyclododecanol can be easily converted to a lactum compound, lactone compound or a dicarboxylic acid compound by a conventional method and thus are important intermediate materials for producing synthetic resins or fibers of polyamide 12 and polyesters.
2. Description of the Related Art
As a process for producing cyclododecanone and cyclododecanol by a catalytic reaction of epoxycyclododecane compounds with hydrogen, J. Mol. Catal., Vol 169, pp 95-103 (1991) discloses a catalytic hydrogenating reaction of 2-epoxy-5,9-cyclododecadiene with hydrogen. In this reaction of the reference, 1,2-epoxy-5,9-cyclododecadiene is brought into contact with hydrogen in the presence of a palladium-carrying catalyst at a reaction temperature of 90xc2x0 C. under a hydrogen gas pressure of 1,275 kPa (13 kg/cm2) on gauge, and epoxycyclododecane is produced as a principal reaction product. Cyclododecanol is produced as a by-product in a yield of 4% and no cyclododecanone is produced. Also, the Draft of 24-th Symposium xe2x80x9cDevelopment of Reaction and Synthesis, Nov. 5-6, 1998, pp 68, discloses a process of catalytic reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a palladium catalyst at room temperature under the ambient atmospheric pressure. In this process, epoxycyclododecane is produced as a principal product, cyclododecanol is produced, as a by-product, in a yield of 5%, and no cyclododecanone is produced.
Further, Neftekhimiya, 16 (1), 114-119 (1976) discloses a catalytic reaction of 1,2-epoxy-5,9-cyclododecadiene with hydrogen in the presence of a palladium-carried catalyst at a reaction temperature of 140xc2x0 C. under a hydrogen gas pressure of 8,106 kPa (80 atmospheres). In this reaction, epoxycyclododecane was produced in a yield of 49.5%, cyclododecanol in a yield of 33.3%, and cyclododecanone in a yield of 3.4%.
In view of the prior arts, a method enabling both cyclododecanone and cyclododecanol to be produced, each in a satisfactory yield from epoxycyclododecane compounds, has not yet been provided.
An object of the present invention is to provide a method of producing cyclododecanone and cyclododecanol from epoxycyclododecane compounds with satisfactory yields thereof.
The above-mentioned object can be attained by the method of producing cyclododecanone and cyclododecanol of the present invention, which comprises bringing an epoxycyclododecane compound and hydrogen into contact with each other in the presence of a solid catalyst comprising:
(a) a catalytic component comprising at least one platinum group metal;
(b) a promoter component comprising at least one member selected from the group consisting of VIII group, Ib group, IIb group, IIIb group, IVb group, Vb group, VIb group and VIIb group elements, and lanthanoid elements and compounds of the above-mentioned elements; and
(c) a carrier on which the catalytic component and the promoter component are supported, to thereby hydrogenate the epoxycyclododecane compound and produce cyclododecanone and cyclododecanol.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the epoxycyclododecane compound is preferably selected from the group consisting of monoepoxycyclododecadiene, monoepoxycyclododecene and monoepoxycyclododecane.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the promoter component (b) of the solid catalyst preferably comprises at least one member selected from the group consisting of nickel metal, iron metal, copper metal, iron(III) nitrate, iron(III) chloride, iron(II) chloride, iron(II) sulfate, triiron tetraoxide, iron(III) hydroxide, cobalt nitrate, cobalt bromide, cobalt oxide, cobalt hydroxide, nickel nitrate, nickel oxide, nickel hydroxide, copper nitrate, copper acetate, silver oxide, gold hydroxide, yttrium chloride, titanium chloride, vanadium oxide, tungsten oxide, molybdenum oxide, manganese nitrate, rhenium oxide, zinc nitrate, zinc chloride, zinc hydroxide, cadmium nitrate, cadmium oxide, mercury oxide, cerium oxide, samarium chloride, dysprosium chloride, and ytterbium oxide.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the carrier (c) of the solid catalyst preferably comprises an inert inorganic material selected from the group consisting of activated carbon, xcex1-alumina, xcex3-alumina, silica, silica-alumina, titania, zeolite and spinel.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the catalytic component (a), for the solid catalyst is preferably present in an amount of 0.01 to 20% by weight, based on the weight of the inert carrier.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the metal atomic ratio (a)/(b) of the catalytic component (a) to the promoter component (b) for the solid catalyst is preferably 10,000:1 to 1:4.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the solid catalyst is preferably present in a molar amount, in terms of the platinum group metal, of 0.00001 to 0.1 times the molar amount of the epoxycyclododecane compound.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the hydrogenation reaction of the epoxycyclododecane compound with hydrogen in the presence of the solid catalyst is preferably carried out at a reaction temperature of 60 to 250xc2x0 C. under a hydrogenr gas pressure of 98 to 14,710 kPa on gauge.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the hydrogenation reaction of the epoxycyclododecane compound with hydrogen is preferably carried out in an organic liquid medium comprising at least one member selected from the group consisting of n-hexane, n-heptane, n-tetradecane, cyclohexane, tetrahydrofuran, dioxane, methyl alcohol, ethyl alcohol, tertiary butyl alcohol, tertiary amyl alcohol, ethyl acetate and butyl acetate.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the liquid medium is preferably employed in an amount not exceeding 20 times the weight of the epoxycyclododecane compound.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the platinum group metal is preferably palladium.
In the method of producing cyclododecanone and cyclododecanol of the present invention, the promoter for catalyst preferably comprises at least one member selected from the group consisting of VIII group, Ib group and IIb group elements, lanthanoid elements, and compounds of the elements.
In the method of the present invention, an epoxycyclododecane compound and hydrogen are brought into contact with each other in the presence of a specific solid catalyst, to produce cyclododecanone and cyclododecanol.
The epoxycyclododecane compound usable as a starting material for the method of the present invention is defined as an organic compound constituted from a saturated or unsaturated 12-membered cyclic hydrocarbon structure and an epoxy group attached to the cyclic hydrocarbon structure. The epoxycyclododecane compound for the method of the present invention is preferably selected from the group consisting of epoxycyclododecadiene, epoxycyclododecene, and epoxycyclododecane. In the above-mentioned epoxycyclododecane compounds, the epoxy ring structure and double bond structure may be of cis-type of trans type, or of other any type.
The epoxycyclododecane compound subjected to the method of the present invention may be in a trade-available grade or a grade refined by a conventional refining means, for example, distillation.
The solid catalyst usable for the method of the present invention comprises the compounds of:
(a) a catalytic component comprising at least one platinum group metal;
(b) a promoter component comprising at least one member selected from the group consisting of VIII group, Ib group. IIb group, IIIb group, IVb group, Vb group, VIb group and VIIb group elements, and lanthanoid elements and compounds of the above-mentioned elements; and
(c) a carrier on which the catalytic component and the promoter component are supported, to thereby hydrogenate the epoxycyclododecane compound and produce cyclododecanone and cyclododecanol.
The platinum group metal usable for the catalytic component (a) of the solid catalyst is one of the platinum group elements, for example, ruthenium, rhodium, palladium, osmium, iridium and platinum and is preferably palladium.
The catalyst component (a) is supported together with a promoter component (b) on a carrier (c), preferably a inert carrier to form a solid catalyst for the reaction of the present invention. The promoter component (b) of the solid catalyst comprises at least one member selected from the group as defined above. Each element can be used in the state of a metal or a compound.
Preferably, the promoter (b) for the solid catalyst comprises at least one member selected from the group consisting of VIII group, Ib group and IIb group elements, lanthanoid elements, and compounds of the VIII group, Ib group, IIb group and lanthanoid elements.
The compounds of the above-mentioned elements for the promoter (b) include nitrates, sulfates, organic acid salts, halides, oxides and hydroxides of the above-mentioned elements.
Particularly, the promoter component (b) of the solid catalyst may comprise at least one member selected from the group consisting of nickel metal, iron metal, copper metal, iron(III) nitrate, iron(III) chloride, iron(II) chloride, iron(II) sulfate, triiron tetraoxide, iron(III) hydroxide, cobalt nitrate, cobalt bromide, cobalt oxide, cobalt hydroxide, nickel nitrate, nickel oxide, nickel hydroxide, copper nitrate, copper-acetate, silver oxide, gold hydroxide, yttrium chloride, titanium chloride, vanadium oxide, tungsten oxide, molybdenum oxide, manganese nitrate, rhenium oxide, zinc nitrate, zinc chloride, zinc hydroxide, cadmium nitrate, cadmium oxide, mercury oxide, cerium oxide, samarium chloride, dysprosium chloride, thulium chloride, thulium oxide, and ytterbium oxide.
The carrier (c) for the solid catalyst comprises an inert inorganic material preferably selected from the group consisting of activated carbon, xcex1-alumina, xcex3-alumina, silica, silica-alumina, titania, zeolite and spinel. More preferably, xcex1-alumina and xcex3-alumina are employed for the carrier.
In the solid catalyst, the catalytic component (a) comprising at least one platinum group metal is preferably present in an amount of 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the weight of the inert carrier.
The platinum group metal of the catalytic component (a) may be supported on the surface or in the inside of the carrier (c) or on the surface and in the inside of the carrier (c).
In the solid catalyst, the metal atomic ratio (a)/(b) of the catalytic component (a) to the promoter component (b) for the solid catalyst is preferably 10,000:1 to 1:4, more preferably 5,000:1 to 1:3.
In the method of the present invention, the solid catalyst is preferably employed in a molar amount, in terms of the platinum group metal, of 0.00001 to 0.1 time, more preferably 0.00005 to 0.01 time the molar amount of the epoxycyclododecane compound.
In the method of the present invention, the hydrogenation reaction of the epoxycyclododecane compound with hydrogen in the presence of the solid catalyst is preferably carried out at a reaction temperature of 60 to 250xc2x0 C., more preferably 80 to 230xc2x0 C. still more preferably 100 to 200xc2x0 C. under a hydrogen gas pressure of 98 to 14,710 kPa, more preferably 196 to 9,807 kPa, still more preferably 196 to 4,903 kPa on gauge.
When the reaction temperature is too high, a yield of a by-product having a high boiling temperature may unpreferably increase. When the reaction temperature and the hydrogen pressure are too low, the reaction rate, namely the production rate of cyclododecanone and cyclododecanol may undesireably decrease.
In the method of the present invention, the hydrogenation reaction system optionally contains an organic liquid reaction medium. The organic liquid medium preferably comprises at least one member selected from the group consisting of hydrocarbons, for example, n-hexane, n-heptane, n-tetradecane and cyclohexane; ether compounds, for example, tetrahydrofuran and dioxane; aliphatic alcohol compounds, for example, methyl alcohol, ethyl alcohol, tertiary butyl alcohol, and tertiary amyl alcohol; and ester compounds, for example, ethyl acetate and butyl acetate.
These liquid compounds may be employed alone or in a mixture of two or more thereof.
The liquid medium is preferably employed in an amount not exceeding 20 times, more preferably not exceeding 10 times the weight of the epoxycyclododecane compound.
After the hydrogenation reaction of the epoxycyclododecanone compound with hydrogen is completed, the target cyclododecanone and cyclododecanol are easily collected from the reaction mixture by a conventional separating procedure, for example, distillation.